3-arylamino-1-8-naphthsultam compound and process of making the same



WILHELM 'NEELMEIER, OF LEVERKUSEN,

AND rnnonon no'orcnn or WIESDORF, GER;

MANY, Assrenoias To GENERAL ANILINE woRKs, INC., on NEW YORK, N. Y A

CORPORATION OF DELAWARE 3-A'RYLAMINO4-8-NAPHTI-ISULTAM comrormn AND ,Pnoonss "or MAKING THE SAME no Drawing. Application filedlluly 21, 1926, Serial No. 12 1,091 and in Gaming m 28, 1925.

Our invention consists in acting With an arylamine upon a 1-8-naphthsultam-3-sulfonic acid compound and in the novel 3- arylamino l 8 naphthsultam compounds ob- :Btained. H

By this reaction the sulfo group in 3 position is replaced by anarylamino group with liberation of sulfurdioxid. The reactionis effected by heating to elevated temperatures in and preferably'in presence of a salt of the arylamine. Thedegree of heating and other particular reaction conditions are of course to a certain extent dependent upon the specific arylainine and naphthsultanr compound 35 used. The reaction can also be carried out inpresence of suitable solvents or diluents.

1e arylarnines of the benzene and nap'ththalene series are particularly suitedfor carrying outour invention; i

In using the l-8snaphthsultarn-3-sulfonic acid itself 3-arylamino-naphthsultams are obtained and from the 1-8-naphthsulta1n-3-6-disulfonic" acid 8-ary1arnino-I-8- inaphthsulta1n-6-sulfonicV acid can be produced; In" using the 1-8Tnaphthsu'ltamr3- (4c?)-6-trisulfonic acid, inwhich the position of one of the suite groups is uncertain,-

as described in the Berichte der Deutschen Qhemischen Gresellschaft, vol. 27, page 2149 a (1894:), 3-arylamino-1-8-napbthsultam 6 sultonic acidsare similarly obtained With elimination of the-labile sulfo group.

Our'novel S-arylamino 1-8-naphthsultam compounds are of thegeneral formula:

- V SO;NX i

aryl group which maybe substituted, X represents hydrogen, alkyl, or acidyl; and 1 represents hydrogenor a sulin which R is an v ionic acid group. i We found 13-arylarnino-1-8-naphthsul- They form salts with organic and inorganic bases, which are of Well crystallized.

The sultam NH group caneasily be acetylated or-alkylated to form the coresponding l-N-alkyl (or o acyl) -3-arylamino-1-8-naphthsultain compound. 1

Some typical 3-arylamino-1-8-naphthsulduced by reacting With 1-8-naphthsultam- 3-'6-disulfonic acid upon aniline,-the toluidines, p-anisidine; etc. The novel products obtained can be represented by the formulas 1-8-naphthsultan1-3 6-disulfonic "acid (deyellowicolorand usually taln-fi-sulfonicacid compounds are those pro- MATES P EN F E? The following example Willfurther illusscribed by Dressel and Kothe in Berichte der Deutschen Chemischen Gesellschaft, vol. 27, page 2149, 1894:) are heated with 1200 parts aniline and 200 parts 19 A; B. hydrochloric acid to 130-ll0 C. The reaction product is poured into a mixture of ice and excess hydrochloric acid. The aniline salt of the 3- phenylamino-l-S-naphthsultam 6 sulfonic acid separates and is filtered off. It can be purified by crystallization from Very dilute acetic acid and is then obtained as small prisms, melting at 277 78 C. It is easily soluble in acetic acid and alcohol, and diificultly soluble in Water.

Dilute caustic soda or sodium acetate solution decomposes the aniline salt; after removing the aniline from the solution and salting out, the crystallized sodium salt is obtained, which is a yellowish powder, easily soluble in water and alcohol. The barium salt is difiicultly soluble, whereas the potassium salt, which crystallizes in yellow prisms is easily soluble and can be used for purifying the compound.

We claim 1. As new products LS-naphthsultam compounds, corresponding probably to the following formula:

y NH.R"

wherein X stands for hydrogen, alkyl, or acidyl, R for an aryl residue which may be substituted, y for hydrogen or a sulfonic acid group, which are in the dry state, yellow crystalline powders easily soluble in acetic acid and alcohol.

2. As new products 1.8-naphthsultam compounds, corresponding probably to the following formula:

\NH.R

wherein 2 stands for hydrogen or a sulfonic group and R stands for an aryl residue which may be substituted, which. are in the dry state yellow crystalline powders easily soluble in acetic acid and alcohol;

3. As new products LS-naphthsultam compounds, corresponding probably to the following formula:

CO E wherein B may be substituted, which are in the dry state yellow crystalline powders easily 3 soluble in acetic acid and alcohol.

5. As a new product the 3-phenylamino-L8- naphthsultam-6-sulfonic acid of the formula:

SOr-NH Maw NE which forms an. aniline salt crystallizing in small prisms melting at 27 7 to 278 C., easily soluble in acetic acid and alcohol, diflicultly soluble in water, forming a diflicultly soluble barium salt, and a potassium salt crystallizing in yellow, easily soluble prisms.

6. A process. of making -arylamino-LS- naphthsultam-G-sulfonic acids which comprises reacting upon a 1.8-naphthsultam-3.6- disulfonic acid with a primary aromatic amine. 7. A process of making 3-arylamin0-1.8- naphthsultam-6-sulfonic acids which comprises reacting upon a 1.S-naphthsultam-3.6- disulfonic acid with a primary aromatic amine in the presence of a salt of said amine.

8 A process of making 3-phenylamino-L8- naphthsultam-G-sulfonic acid which comprises reacting upon aniline with 1.8-naphthsultam-3.6-disulfonic acid in the presence of hydrochloric acid at a temperature of about13O1 l-O C.

9. A process of making 3-arylamino-L8- naphthsultam compounds which comprises reacting with a primary aromatic amine upon a 1.8-naphthsultam-3-sulfonic acid compound, which may be substituted by further sulfonic acid groups.

10. A process of making 3-arylamino-L8- J naphthsultam compounds which comprises reacting upon a 1.8maphthsultam-3-sulfonic acid compound, which may be substituted by further sulfonic acid groups, with a primarv aromatic amine in the presence of a said amine.

In testimony whereof, we aflix our signatures.

VVILHELM NEELMEIER. THEODOR NOCKEN.

salt of the 

